Process for the production of metal compounds of azo-dyestuffs on animal fibers



Patented Nov. 15, 1932 warren stares PATENT orrics FRITZ STRAUB, BASEL, AND HERMANN SCHNEIDER AND HEINRICH BEfllitll'HAlRZD, OF

RIEHEN, NEAR BASEL, SWITZERLAIID, ASSIGNORS TO THE'FIRM CAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND SOCIETY OF CHEMI! rnocuss FOR THE PRODUCTION or METAL COMPOUNDS or azo-nxn's'rurrson Alum rnannsv No Drawing. Original application filed September ld,1928, Seria1 No. 305,135, and in: Switzerland 1 September 17, 1927. Divided and this application. filed June 23, 1931. Serial No. 546,420.

The present. invention relates to the production of metal compounds of azo dyestu'iis on animal fibers.

By the present invention valuable products-which may be defined as mixed azodyestuffs containing metal's-are-obtained by causing agents yielding metal to react on mixtures of such azo-dyestuifs which contain groups capable of fixing metal, or by causing already metallized azo-dyestufls to react on not metallized azo-dyestufis containing groups capable of fixing metal, these not metallized dyestuffs being identical with or different from the starting dyestulf of the metallized product. Thus there-are obtained complex metal compounds which may contain one or more metals and one or more azodyestuffs. The new complex-es may contain only monoazo-dyestufls or only polyazo-dyestuffs, or monoazo-dyestufis together with polyazo-dyestulfs.

The reaction may occur in neutral, acid or alkaline medium under atmospheric pressure or under increasedpressure and in presence or absence of suitable additions, such'as organic or inorganic salts or substances of another kind, such as organic solvents.

As suitable metals there come into consideration those which are at least bivalent and which are further capable of yielding complex compounds. These metals may be used in the form of salts, oxides orhy'droxides. Also the complex metal compounds which these compounds may form with dyestuffs containing groups capable of binding metal may be used as agents yielding metal. All these agents yielding metal may be used single or as mixtures.

The new products may also be'made by performing the operation of coupling which produces the dyestuff or dyestuffs in presence of anagent yielding metal.

Finally the new products may the dye-bath or onthefiber.

' The dyestufi's obtained by the invention be made in are usefulnot only for dyeing w l or cotton, but also for dyeing or coloring leather, varnishes and other materials.

The formula of these metal compounds is not known. I The following examples illustrate the invention, the parts being by weight 1 Example I 1 10 parts of the chromium compound of the dyestuif from diazotized i-amino-Q-hydroxynaphthalene-d-sulfonic acid and wnaphthol of the formula l naphthol of the formula No, on v on A suspension, which has been'boiled for a short time, of 45- parts of the dyestufl from the nitrated diazo-compound of l-amino-2- hydroxynaphthalene-4-sulfonic acid and ,8- naphthol of the formula I S 0 3H nitrated and'lQ parts of the reduction product of the said dyestuff in 600 parts of water are mixed with parts of crystallized sodium acetate and parts ofa solution of chromium formate containing 41 per cent. of Gr O and the mixture is boiled for a long time in a refiux apparatus. 360 parts of saturated common salt solution are then added and boiling continued for 15 hours, after. which time .chroming is complete. By salting out the 10 parts of the chromium compound of the azo-dyestuff from 1-amino-2-hydroxynaphthalenel-sulfonic' acid and a-liydroxynaphthalene are dissolved in 250 parts of water, while boiling. To this solution there are added 2.37 parts of the dyestuff from diazotized Q-amino-l-hydroxynaphthalene- The mixture in solution thus obtained is slightly acidified by means of acetic acid and boiled for a long time in a. reflux apparatus.

The new dyestuff thus obtained is then sepafuric acid to a green-blue solution. The formula of this chromium compound is not known. It dyes wool and silk in blue tints which are exceedingly fast.

- Example 4' 7 .88 parts of the azo-dyestuif from l-amino- Q-hydtoxynaphthalenel-sulfonic acid and fi-hy'droxynaphthalene of the formula and 4.74 parts of the dyestuif from Q-amino- 1-hydroxynaphthalene-4-sulfonic acid and ,B-hydroxynaphthalene of the formula HOaS -OH OH are dissolved in 300 parts of water, While boiling. To this solution there are then added 12 parts of Cr O in the form of a solution containing 4, per cent. by volume of chromium fluoride, and the reaction mixture is boiled for some time, in a reflux apparatus. The dyestufi thus obtained is separated in usual manner. It forms a blackish powder which dissolves in Water to a violet, in caustic soda solution of 10 per cent. strength to a redviolet, and in concentrated sulfuric acid to a blackish-blue solution. The formula of this chromium compound is not known. It dyes Wool and silk from an acid bath fast blue tints.

Example 5 7.88 parts of the azo=dyestuff from l-amino- 2-hydroxynaphthalene-4-sulfonic acid and ,81hydroxynaphthalene, and 4.? parts of the dyestuif from 4-.chloro-2-amino-l-phenol and 1: S-dihydroxynaphthalene 3 :6 disulfonic acid of the. formula OH OH SOaH 7 are together dissolved in 300 parts of water, while boiling. To this solution there are then added 12 parts of Cr O in the form of a solution containing 4 per cent. by volume of chromium fluoride, and the reaction mixture is boiled for a long time in a reflux apparatus. The new dyestuff is separated in usual manner. It forms a blackish powder which dissolves in water to a blue, a caustic soda solution of 10 per cent. strength to a reddish-blue, and in concentrated sulfuric acid to a blackish solution. The formula of this chromium compound is not known. It dyes wool and silk from a hath made acid Gil ivith sulfuric acid or acetic acid fast blue tints.

I Example 6 5.8 parts of the monoazo-dyestufi from 1- amino 2 hydroxynaphthalene 4 sulfonic acid and 2-phenylamino-5-hydroxynaphtha lerie-T-sulfonic acid of the formula HOaS- NHO H035 N=N and 8.4 parts of the diazo-dyestuff from 2 mol diazotized 2-an1ino-l-phenol--sulfamide and 1 mol 5: 5-dihydroXy-2:2-dinaphthylamino-7 7 -disulfonic acid of the formula SO -NE:

are together dissolved in 400 parts of water. After addition of a solution of chromium fluoride corresponding to 6 parts of C1' O the Whole is boiled for a long time in a reflux apparatus. The new metal compound is obtained by evaporation and salting out.- It dissolves in Water to a blue, in dilute caustic soda solution to a reddish-blue, and in concentrated sulfuric acid to a violet solution. The formula of this chromium compound is not known. The dyestuff forms a dark powder and dyes silk and Wool from a bath made acid with acetic acid and viscose and cotton from a neutral bath blue tints.

Example 7 8.4 parts of the disazodyestuff from 2 mol 2-amino-l-phenoll-sulfamide and1mol5 5- dihydroxy 2 2 dinaphthylamino -7': 7 di sulfonic acid and 9.3 parts of the disazodyestulf from 2 mol t-nitro-6-sulfo-2-aminothe formula fluoride corresponding to 12 parts'ef Cr O and the whole is heated for some hours While 7 substituting the evaporated Water. The new chromium compound is obtained by concen tration and salting out. The formula of this a dark powder which dissolves in Water to a blue, in dilute caustic soda solution to a reddish-blue and in concentrated sulfuric acid to a reddish-blue solution, dyeingsilk, viscose and cotton blue tints.

7 Example 8 A dye-bath is prepared With (calculated in each case on theweight of the Wool) 7 per cent. of the chromium compound of the azodyestulf from diazotized 2-amino-l-hydroxy- S Or-NH! thol of the formula no n 01-1 .70 chromium compound is not know It i 1 per cent. of the chromium compound of the azo-dyestufl' from diazotized 1-amino-2-hydroxynaphthalenel-sulfonic acid and 1 (3- sulfamido) -plienyl-3-methyl-5-pyrazolone of SO NHz OH l-phenol and 1 mol 5: 5-dihydroXy-2:2-dinaphthylamino-7 7-disulfonic acid of the formula SOzH No i Ems OH no3s NH SOaH l l lo: )H

are together dissolved in 500 parts of Water.

2 per cent. of the azo-dyestulf from diazotized To this there is added a solution of chromium 4; chloro -2- amino l-phenol and 1: S-dihydroXynaphthalene-3 6disulfonic acid of the formula 1 on on on 10 per cent. of Glaubers salt and 2 per cent. of concentrated sulfuric acid.

Example 9 A dyebath is prepared with (calculated on the weight of the goods) 2. 1% per cent. of the chromium compound of the azo-dyestuff from diazotized l-amino 2 hydroxynaphthaleneet-sulfonic acid and fi-naphthol of the formula 0.6 per cent of the azodyestufi' from diaZotized 5-nitro-2-amino1-phenol and 2-aminonaphthalene-G-sulfonic acid of the formula 0 H ITIHz 10 per cent. of Glaubers salt and 2 per cent. of acetic acid, 100 parts of wool are entered at C. and this temperature is maintained for 20 minutes and then raised to boiling; 2 per cent. of concentrated sulfuricacid are added, boiling is continued for half an hour and there are added another 6 per cent. of concentrated sulfuric acid, whereupon dyeing is continued by boiling for 11 hours. The goods are then washed and dried. The wool is dyed marine-blue tints of very good properties of fastness.

Instead of chromium other metals which are at least bivalent and which are further capable of yielding complex compounds may be used, such as iron, copper, manganese, nickel, cobalt, vanadium, uranium, titanium, tin or aluminium. Also more than one of these metals may be used together.

What we claim is 1. A process for the production of metal compounds of azo-dyestufis .on animal fibers,

consisting in causing ortlio-liydroxy-azo-dye= stuffs and metal compounds of orthy-hys droXyaZo-dyestuffs of metals which are at least bivalent, and which are capable of forming complex compounds, to reacton each 1 dyestufi's of metals which are at least bivalent and which are capable of forming complex compounds, to react on each other in presence of wool.

3. A process for the production of chromium compounds of azo-dyestuflfs on wool,

consisting in causing ortho-hydroxy-azo-dyestuffs and chromium compounds of ortho-hydro-Xy-azo-dyestuffs to react on each other in presence of wool.

4. A process for the production of a chromium compound of an aZo-dyestufl on wool, consisting in causing the azo-dyestuff from diazotized d-chloroQ-amino-l-pl1enol and l 8 dihydroxynaphthalene 3: 6 -disulfonic acid, the chromium compound of the azo-dyestufi from diazotized 2-amino-l-hydroxynaphthalene-4e S-disulphonic acid and ,8- naphthol, and the chromium compound of the azo-dyestuff from diazotized l-amino-Q-hydroxynaphthalene--sulfonic acid and 1 (3- sulfamido) phenyl 3 methyl 5 pyrazolone, to react on each other in the presence of wool. In witness whereof we have hereunto signed our names this 15th day of-June, 1931.

FRITZ STRAUB. HERMANN SCHNEIDER. HEINRICH BERN HARD. 

